US10927233B2 - Stabilized plasticizers for thermoplastic polyurethane - Google Patents
Stabilized plasticizers for thermoplastic polyurethane Download PDFInfo
- Publication number
- US10927233B2 US10927233B2 US15/115,285 US201515115285A US10927233B2 US 10927233 B2 US10927233 B2 US 10927233B2 US 201515115285 A US201515115285 A US 201515115285A US 10927233 B2 US10927233 B2 US 10927233B2
- Authority
- US
- United States
- Prior art keywords
- thermoplastic polyurethane
- acid esters
- composition
- carbodiimides
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 111
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 111
- 239000004014 plasticizer Substances 0.000 title abstract description 25
- -1 aliphatic carbodiimides Chemical class 0.000 claims abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 61
- 150000002148 esters Chemical class 0.000 claims abstract description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 24
- JBGDSVVIBTXYJD-UHFFFAOYSA-N 2-hydroxy-4-oxopentane-1,2,3-tricarboxylic acid Chemical class CC(=O)C(C(O)=O)C(O)(C(O)=O)CC(O)=O JBGDSVVIBTXYJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 150000003021 phthalic acid derivatives Chemical class 0.000 claims abstract 4
- 150000001278 adipic acid derivatives Chemical class 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000010348 incorporation Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 150000003022 phthalic acids Chemical class 0.000 description 20
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 14
- 150000001279 adipic acids Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 0 [1*]OC(CC(=O)O[2*])(CC(=O)O[4*])C(=O)O[3*] Chemical compound [1*]OC(CC(=O)O[2*])(CC(=O)O[4*])C(=O)O[3*] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- UTFSEWQOIIZLRH-UHFFFAOYSA-N 1,7-diisocyanatoheptane Chemical compound O=C=NCCCCCCCN=C=O UTFSEWQOIIZLRH-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- QJJVAUMJKWWKTD-UHFFFAOYSA-N 2-[(3,4-dichloro-5-methyl-1H-pyrrole-2-carbonyl)amino]-4-phenylmethoxy-1,3-benzothiazole-6-carboxylic acid Chemical compound C(C1=CC=CC=C1)OC1=CC(=CC2=C1N=C(S2)NC(=O)C=1NC(=C(C=1Cl)Cl)C)C(=O)O QJJVAUMJKWWKTD-UHFFFAOYSA-N 0.000 description 1
- JJHAVEZWJHDLIT-UHFFFAOYSA-N 2-[2-(4-ethyl-2-oxooctan-3-yl)oxy-2-oxoethyl]-2-hydroxybutanedioic acid Chemical compound CCCCC(CC)C(C(C)=O)OC(=O)CC(O)(C(O)=O)CC(O)=O JJHAVEZWJHDLIT-UHFFFAOYSA-N 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- KMHZPJNVPCAUMN-UHFFFAOYSA-N Erbon Chemical compound CC(Cl)(Cl)C(=O)OCCOC1=CC(Cl)=C(Cl)C=C1Cl KMHZPJNVPCAUMN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- KAEIHZNNPOMFSS-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1CCC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1CCC1=CC=CC=C1 KAEIHZNNPOMFSS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940100573 methylpropanediol Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/095—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to carbodiimide or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/346—Polycarboxylic acids having at least three carboxylic acid groups having four carboxylic acid groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/18—Plasticising macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Definitions
- the present invention relates to a process for producing a thermoplastic polyurethane, comprising the provision of a composition Z(W) comprising at least one carbodiimide selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides, polymeric aliphatic carbodiimides, monomeric aromatic carbodiimides, oligomeric aromatic carbodiimides and polymeric aromatic carbodiimides, and at least one ester selected from the group consisting of citric acid esters, acetyl citric acid esters, phthalic acid esters, benzoic acid esters, adipic acid esters, hydrogenated phthalic acid esters and phosphoric acid esters; and the subsequent addition of the composition Z(W) to a thermoplastic polyurethane or to a reaction mixture for producing a thermoplastic polyurethane.
- a composition Z(W) comprising at least one carbodiimide selected from the group consisting of monomeric aliphatic car
- the present invention relates to a thermoplastic polyurethane obtainable or obtained by a process according to the invention and to the use of the composition Z(W) as plasticizer for thermoplastic polyurethanes.
- the present invention also relates to moldings comprising a thermoplastic polyurethane according to the invention.
- Plasticized thermoplastic polyurethanes are widely known and are described, for example, in DE 10 2005 040 131 or EP 1 338 614.
- Thermoplastic polyurethanes of this kind comprise at least one plasticizer.
- the plasticizer it is to be ensured particularly that the product is compatible with the thermoplastic polyurethane, the plasticizer has a sufficiently good plasticizing effect and that the plasticizer does not bring with it a negative influence on, for example, resistance to water and other media.
- thermoplastic polyurethanes are often phthalates and benzoates for polyester-TPU or phosphates for polyether-TPU. Systems of this kind are disclosed, for example, in EP 1 556 433 or EP 0 134 455. Furthermore, known plasticizers are selected from the group of adipates, hydrogenated phthalates, fatty acids or citric acid esters, with the latter being disclosed, for example, in EP 1 108 735 or WO 2010/125009.
- thermoplastic polyurethanes It is known from the prior art that pure citric acid esters have a very good plasticizing effect in thermoplastic polyurethanes.
- WO 2010/125009 discloses a corresponding plasticizer for thermoplastic polyurethanes.
- pure citric acid ester has the disadvantage of a low thermal resistance, for example even at temperatures as arise during the production and the processing of these esters as well as the incorporation of these esters into thermoplastic polyurethane.
- acetylbutyl citrate can sometimes thermally decompose in such a way that a considerable increase in the acid number is measurable.
- thermoplastic polyurethane If a plasticizer damaged in this way is incorporated into thermoplastic polyurethane, this has a negative effect on the resistance of the plasticized thermoplastic polyurethane. This can lead to, for example, the hydrolysis resistance of a thermoplastic polyurethane plasticized in this way being considerably impaired.
- thermoplastic polyurethanes which have adequate resistance to thermal degradation. It was a further object of the present invention to provide plasticizers for thermoplastic polyurethanes which have an adequate hydrolysis stability.
- thermoplastic polyurethanes using plasticizers of this kind.
- thermoplastic polyurethane comprising the steps
- the present invention relates to a process for producing a thermoplastic polyurethane comprising the steps (i) and (ii).
- a composition Z(W) is provided which has at least one carbodiimide, and at least one ester as defined above.
- the composition Z(W) is added to a thermoplastic polyurethane or a reaction mixture for producing a thermoplastic polyurethane.
- the composition is added to a fully reacted thermoplastic polyurethane or to a reaction mixture for producing a thermoplastic polyurethane.
- composition Z(W) is added to a reaction mixture, this can in principle take place at any stage in the production process of a thermoplastic polyurethane.
- composition Z(W) is added to an essentially fully reacted thermoplastic polyurethane, this can take place for example by means of incorporation by compounding or incorporation by swelling.
- the present invention accordingly also relates to a process as described above where the composition Z(W) is added according to step (ii) to a thermoplastic polyurethane by means of incorporation by compounding or incorporation by swelling.
- composition Z(W) according to the invention, a stabilization of the ester selected from the group consisting of citric acid esters, acetyl citric acid esters, phthalic acid esters, benzoic acid esters, adipic acid esters, hydrogenated phthalic acid esters and phosphoric acid esters is achieved through the addition of a carbodiimide-containing stabilizer, and the resulting increase in the acid number of the ester can be considerably reduced for the same thermal stress.
- the acid number serves here as a measure of the thermal degradation of the ester.
- the increased acid number simultaneously has a negative effect on the hydrolytic stability of the resulting plasticized thermoplastic polyurethane.
- a further advantage of the systems according to the invention is also the considerably improved resistance to hydrolytic degradation.
- a plasticized thermoplastic polyurethane using the composition Z(W) according to the invention has, according to the examples, a hydrolysis stability of 56 days.
- a thermoplastic polyurethane comprising a non-stabilized variant by contrast, only has a hydrolysis stability of 35 days, according to the examples.
- the stabilization according to the invention it is thus possible firstly to increase the thermal stability of an ester-based plasticizer.
- the stabilization of the plasticizer it is also possible to produce a plasticized thermoplastic polyurethane with considerably improved hydrolysis stability.
- this effect is attributed to the order of addition according to the invention, i.e. a provision of the composition Z(W) and a subsequent addition to the thermoplastic polyurethane.
- thermoplastic polyurethane comprises the provision of a composition Z(W) comprising
- composition Z(W) here can be obtained in all ways known to the person skilled in the art, for example by mixing the component. According to the invention, the mixing can take place by means of standard processes.
- the composition Z(W) can be produced directly prior to addition to the thermoplastic polyurethane.
- the production of the composition Z(W) in the context of the present invention involves the mixing of the components and a setting of the acid number.
- the setting time here is up to 30 minutes.
- the composition Z(W) according to the invention is storage-stable and can also be further processed at a considerably later time with properties according to the invention.
- the present invention accordingly also relates to a process as described above where the production of the composition Z(W) involves the mixing of the components and a setting of the acid number.
- the present invention according to a further embodiment also relates to a process as described above where the addition of the composition Z(W) takes place according to step (ii) after the setting has concluded.
- composition Z(W) comprises at least one ester selected from the group consisting of citric acid esters, acetyl citric acid esters, phthalic acid esters, benzoic acid esters, adipic acid esters, hydrogenated phthalic acid esters and phosphoric acid esters.
- the composition Z(W) can also comprise mixtures of two or more of the specified esters.
- esters are those which have adequate compatibility with the thermoplastic polyurethane used and achieve a plasticizing effect. Furthermore, esters are suitable which can be processed under reaction conditions that are usually present during the synthesis and processing of thermoplastic polyurethanes, i.e. esters which have an adequate stability at a temperature in the range of up to 250° C.
- a compatibility suitable according to the invention is, for example, in the range from 15 to 50%, where the compatibility of the ester with the thermoplastic polyurethane in the context of the present invention is determined by reference to the transparency of the overall system.
- the overall system in the context of the present invention is transparent, i.e. a homogeneous mixture of the components is present.
- a reduction in the Shore hardness in the range from 3 Shore A to 35 Shore A, preferably in the range from 5 Shore A to 25 Shore A, for example in the range from 6 Shore A to 15 Shore A, is advantageously achieved by the plasticizing properties compared to a thermoplastic polyurethane without the addition of the composition Z(W).
- Suitable esters are known per se to the person skilled in the art as plasticizers for thermoplastic polyurethanes.
- the composition Z(W) comprises at least one ester selected from the group consisting of citric acid esters and acetyl citric acid esters.
- plasticizer compounds based on citric acid esters can carry either no functional groups such as, for example, CITROFOL® B II, or else OH functions such as, for example, CITROFOL® B I or CITROFOL® A I.
- Preferred esters are those of the general formula (I):
- the present invention accordingly also relates to a process as described above where the composition Z(W) comprises at least one citric acid ester.
- the composition Z(W) comprises at least one ester selected from the group consisting of triethyl citrate, tyltriethyl citrate, tri(n-butyl) citrate, acetyltri(n-butyl) citrate and acetyl(2-ethylhexyl) citrate.
- composition Z(W) further comprises at least one carbodiimide selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides, polymeric aliphatic carbodiimides, monomeric aromatic carbodiimides, oligomeric aromatic carbodiimides and polymeric aromatic carbodiimides.
- carbodiimide selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides, polymeric aliphatic carbodiimides, monomeric aromatic carbodiimides, oligomeric aromatic carbodiimides and polymeric aromatic carbodiimides.
- carbodiimides used according to the invention can also vary within wide ranges. Suitable carbodiimides are described, for example, in EP 0 628 541, DE 43 189 79 A1, DE 198 21 666 A1 or EP 1 138 706 B1. Particularly suitable carbodiimides are described, for example, by the general formula (II).
- the present invention accordingly also relates to a process as described above where the composition Z(W) comprises at least one carbodiimide selected from the group consisting of monomeric aliphatic carbodiimides, oligomeric aliphatic carbodiimides and polymeric aliphatic carbodiimides.
- the molar ratio of added carbodiimide groups to the initial acid content of the ester used can vary in wide ranges and, according to the invention, is preferably in the range from 20:1 to 1:10, preferably 10:1 to 1:2.
- the present invention accordingly also relates to a process as described above where the molar ratio of added carbodiimide groups to the initial acid content of the ester used is in the range from 20:1 to 1:10.
- the amount of composition Z(W) used is based on the total amount of thermoplastic polyurethane. According to the invention, this can vary within wide ranges, the composition Z(W) being used in accordance with the invention in amounts which is customary for plasticizers.
- the amount of composition Z(W) based on the total amount of thermoplastic polyurethane is in the range from 1 to 50% by mass, in particular in the range from 2.5 to 40% by mass, preferably in the range from 5 to 35% by mass, and particularly preferably in the range from 7.5 to 30% by mass. If the composition Z(W) is added to a reaction mixture for producing a thermoplastic polyurethane, the amount of composition Z(W) used in the context of the present invention refers to the total amount of structural components used in the thermoplastic polyurethane.
- the present invention accordingly also relates to a process as described above where the amount of composition Z(W) based on the total amount of thermoplastic polyurethane is in the range from 1 to 50% by mass.
- the composition Z(W) is added to a thermoplastic polyurethane or a reaction mixture for producing a thermoplastic polyurethane.
- thermoplastic polyurethanes used can likewise vary within wide ranges.
- Processes for producing thermoplastic polyurethanes are generally known.
- the polyurethanes are produced by reacting (a) isocyanates with (b) compounds reactive towards isocyanates and preferably with (c) chain extension agents, optionally in the presence of (d) catalysts and/or (e) customary auxiliaries.
- the aim below is to explain by way of example preferred starting components and processes for producing preferred polyurethanes.
- the components of (a) isocyanates, (b) compounds reactive towards isocyanates, (c) chain extension agents, and optionally (d) catalysts and/or (e) customary auxiliaries preferred by way of example in the production of these polyurethanes will be described below.
- the isocyanates (a), the compounds (b) reactive towards isocyanate and, if used, also the chain extenders (c) are also discussed as structural components.
- Organic isocyanates (a) that can be used are generally known isocyanates, preference being given to aromatic, aliphatic, cycloaliphatic and/or araliphatic isocyanates, further preferably diisocyanates, preferably 2,2′-, 2,4′- and/or 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and/or 2,6-tolylene diisocyanate (TDI), 3,3′-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylene diisocyanate, tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate-1,5,2-ethylbutylene diisocyanate-1,4-pentamethylene diisocyan
- MDI 2,2′-, 2,4′- and/or 4,4′-diphenylmethane diisocyanate
- NDI 1,5-naphthylene diisocyanate
- TDI 2,4- and/or 2,6-tolylene diisocyanate
- HDI hexamethylene diisocyanate
- H12MDI 4,4′-, 2,4′- and 2,2′-dicyclohexylmethane diisocyanate
- H12MDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane IPDI, especially preferably 4,4′-MDI.
- Chain extension agents (c) that can be used are generally known aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds. Suitable compounds are known to the person skilled in the art. Suitable compounds preferably have groups reactive towards isocyanates, such as e.g. alcohol or amine groups, preferably alcohol groups.
- Suitable catalysts (d), which in particular accelerate the reaction between the NCO groups of the isocyanates (a), preferably of the diisocyanates and the hydroxyl groups of the structural components (b) and (c) are the tertiary amines customary and known according to the prior art, preferably triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N1N′-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo-(2,2,2)-octane and similar as well as in particular organic metal compounds such as titanic acid esters, iron compounds, preferably iron-(MI) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctoate, tin dilaurate and/or tin dialkyl salts, of aliphatic carboxylic acids, preferably dibutyltin diacetate, dibutyltin dilaurate
- auxiliaries are also added to the structural components (a) to (c). Mention may be made, for example, of surface-active substances, flame retardants, germinating agents, oxidation stabilizers, lubricating and mold release aids, dyes and pigments, stabilizers, e.g. against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers and reinforcing agents.
- the structural components (b) and (c) can be varied within relatively wide molar ratios.
- the thermoplastic polyurethane has a characteristic number from 980 to 1200.
- the characteristic number is defined by the molar ratio of isocyanate groups in component (a) used overall in the reaction to the groups reactive towards isocyanates, i.e. the active hydrogens, of components (b) and optionally chain extenders (c).
- the TPU production can be performed by known processes in a continuous manner, preferably using reaction extruders or the belt process according to one-shot or the prepolymer process, or in a discontinuous manner. According to the invention, preference is given to the one-shot process. In these processes, the components (a), (b) and optionally (c), (d) and/or (e) entering the reaction can be mixed in succession or at the same time as one another, in which case the reaction starts directly.
- the structural components (a), (b) and optionally (c), as well as the components (d) and/or (e) are introduced into the extruder individually or as a mixture, and reacted preferably at temperatures from 100° C. to 280° C., further preferably at 140° C. to 250° C.
- the resulting TPU is extruded, cooled and granulated.
- composition Z(W) can be added during or after the production, for example together with the components (d) and/or (e).
- thermoplastic polyurethanes based on polyetherols or polyesterols or mixtures of polyetherols and polyesterols.
- the present invention accordingly also relates to a process as described above where the thermoplastic polyurethane is a thermoplastic polyurethane based on a polyesterol or a polyetherol.
- the thermoplastic polyurethane is based on an MDI as diisocyanate and a polyesterol and/or polyetherol, in particular a polyester of adipic acid with butanediol and/or ethylene glycol and/or methylpropanediol and/or propanediol and/or hexanediol or a polyether based on polyethylene oxide, polypropylene oxide, and polytetrahydrofuran or the mixtures thereof.
- MDI diisocyanate
- a polyesterol and/or polyetherol in particular a polyester of adipic acid with butanediol and/or ethylene glycol and/or methylpropanediol and/or propanediol and/or hexanediol or a polyether based on polyethylene oxide, polypropylene oxide, and polytetrahydrofuran or the mixtures thereof.
- the present invention also relates to a thermoplastic polyurethane obtainable or obtained by a process as described above.
- the thermoplastic polyurethanes according to the invention are characterized by an increased hydrolysis stability.
- composition Z(W) comprising
- thermoplastic polyurethanes particularly during the production of injection molded products, extrusion products or compounds.
- the present invention also relates to moldings comprising a thermoplastic polyurethane obtainable or obtained according to a according to the invention or a thermoplastic polyurethane according to the invention. Furthermore, preference is given to injection molded products or extrusion products as moldings.
- thermoplastic polyurethanes As plasticizer for thermoplastic polyurethanes.
- thermoplastic polyurethanes As plasticizer for thermoplastic polyurethanes.
- the effect according to the invention is not limited to the scavenging of carboxylic acids produced by thermal degradation, i.e. the stabilizing effect does not arise upon the addition of stabilizers with a basic effect which scavenge only the resulting acid.
- Example 3.1 Example 3.2
- Example 3.3 Formulation Freeflex DPGA 15 [fraction in %] Citrofol ® ATBC BII 15 15 [fraction in %] Fraction of 0.435 0.435 0.435 Elastostab ® H01 in overall formulation [%] Type of Elastostab ® Addition of TPU Addition of TPU Premixed with H01 addition synthesis process synthesis process Citrofol ATBC BII Test Standard Unit Result Result Result Standard Density DIN EN g/cm 3 1.187 1.177 1.175 ISO 1183- 1A Shore A DIN 53505 71 72 73 TS longitudinal DIN EN MPas 40 38 40 BE longitudinal ISO 527 % 590 570 590 TPS DIN ISO kN/m 52 53 52 34-1, B (b Abrasion DIN 53516 mm 3 36 18 29 Exposure/artificial aging Hydrolysis resistance 80° C., H2O +56 d 35 d 56 d vapor TS longitudinal 32 MPas 24 MPas
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- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Polyurethanes Or Polyureas (AREA)
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EP14153255 | 2014-01-30 | ||
EP14153255.6 | 2014-01-30 | ||
EP14153255 | 2014-01-30 | ||
PCT/EP2015/051067 WO2015113874A1 (de) | 2014-01-30 | 2015-01-21 | Stabilisierte weichmacher für thermoplastisches polyurethan |
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US10927233B2 true US10927233B2 (en) | 2021-02-23 |
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US (1) | US10927233B2 (hu) |
EP (1) | EP3099725B1 (hu) |
JP (2) | JP2017504706A (hu) |
KR (1) | KR20160113709A (hu) |
CN (1) | CN105940033B (hu) |
BR (1) | BR112016017346A8 (hu) |
ES (1) | ES2729411T3 (hu) |
HU (1) | HUE043480T2 (hu) |
MX (1) | MX2016009951A (hu) |
PL (1) | PL3099725T3 (hu) |
PT (1) | PT3099725T (hu) |
RU (1) | RU2678842C2 (hu) |
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EP4079810A1 (de) | 2021-04-20 | 2022-10-26 | LANXESS Deutschland GmbH | Hydrolysestabile thermoplastische polyurethane, verfahren zur herstellung und deren verwendung |
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EP0628541A1 (de) | 1993-06-08 | 1994-12-14 | BASF Aktiengesellschaft | Carbodiimide und/oder oligomere Polycarbodiimide auf Basis von 1,3-Bis-(1-methyl-1-isocyanatoethyl)-benzol, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Hydrolysestabilisator |
DE19821666A1 (de) | 1998-05-14 | 1999-11-25 | Basf Ag | Carbodiimide auf der Basis von 1,3-Bis-(1-methyl-1-isocyanatoethyl)-benzol |
EP1108735A1 (en) | 1999-12-03 | 2001-06-20 | Bayer Corporation | Liquid, hydrophobic, non-migrating, non-functional polyurethane plasticizers |
EP1338614A1 (de) | 2002-02-23 | 2003-08-27 | Bayer Ag | Verfahren zur Herstellung von weichen, gut entformbaren thermoplastischen Polyurethanelastomeren mit geringer Schwindung |
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WO2010125009A1 (en) | 2009-04-29 | 2010-11-04 | Basf Se | Soft thermoplastic polyurethane based on the ester of tricarboxylic acid |
EP1138706B1 (de) | 2000-03-29 | 2010-12-01 | RHEIN-CHEMIE RHEINAU GmbH | Blockcopolymere auf Basis von Polycarbodiimiden, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Hydrolysestabilisatoren |
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JP2002047421A (ja) * | 2000-07-31 | 2002-02-12 | Toyo Ink Mfg Co Ltd | 劣化防止剤、熱可塑性樹脂組成物、および成形品 |
WO2011141408A2 (de) * | 2010-05-10 | 2011-11-17 | Basf Se | Thermoplastisches polyurethan enthaltend glycerin, das mit mindestens einer aliphatischen carbonsäure verestert ist als weichmacher |
CN104024297B (zh) * | 2011-09-30 | 2016-05-18 | 拜耳知识产权有限责任公司 | 由基于由琥珀酸和1,3-丙二醇形成的聚酯二醇的可热塑性加工的聚氨酯制成的均匀挤出制品 |
CN103102469B (zh) * | 2012-12-18 | 2014-11-05 | 万华化学集团股份有限公司 | 一种高强度高韧性的聚氨酯材料及其制备方法和用途 |
CN103289349A (zh) * | 2013-06-28 | 2013-09-11 | 南通华盛高聚物科技发展有限公司 | 生物降解树脂组合物 |
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JP2020090668A (ja) | 2020-06-11 |
RU2678842C2 (ru) | 2019-02-04 |
WO2015113874A1 (de) | 2015-08-06 |
EP3099725A1 (de) | 2016-12-07 |
HUE043480T2 (hu) | 2019-08-28 |
EP3099725B1 (de) | 2019-03-06 |
JP2017504706A (ja) | 2017-02-09 |
US20170009054A1 (en) | 2017-01-12 |
RU2016135070A3 (hu) | 2018-08-24 |
PL3099725T3 (pl) | 2019-08-30 |
MX2016009951A (es) | 2016-11-11 |
ES2729411T3 (es) | 2019-11-04 |
CN105940033A (zh) | 2016-09-14 |
CN105940033B (zh) | 2021-07-06 |
BR112016017346A8 (pt) | 2020-06-16 |
KR20160113709A (ko) | 2016-09-30 |
PT3099725T (pt) | 2019-06-06 |
TR201906934T4 (tr) | 2019-06-21 |
RU2016135070A (ru) | 2018-03-05 |
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